The Distribution of Total Particulate Matter (TPM) And Nicotine Between Mainstream and Sidestream Smoke in Bidis and Cigarettes

ABSTRACT

The mainstream (MS) and sidestream (SS) smoke of three types of popular Indian cigarettes, a brand of low tar Indian cigarettes, a brand of US cigarettes and two brands of popular Indian bidis were analysed for carcinogenic total particulate matter (TPM) and nicotine levels employing standard smoking conditions and/or modified smoking standards.

The analysis clearly demonstrated relatively higher levels of TPM and nicotine in MS of three types of popular Indian cigarettes when compared with a brand of low tar Indian cigarettes or a brand of US cigarettes or reported values for MS of western cigarettes. This was also reflected in MS/SS ratios of TPM and nicotine as TPM and nicotine levels in SS of Indian and US cigarettes were similar, when tested employing standard smoking conditions.

Comparative analysis of Indian bidis/cigarettes and a brand of US cigarettes employing modified smoking standard (i.e. 2 puffs/min instead of 1 puff/min) revealed significantly lower values of TPM and nicotine in SS of Indian bidis when compared with corresponding values in Indian/US cigarettes. This shows that contribution of TPM and nicotine in SS from a single bidi to environmental tobacco smoke (ETS) is very much less than that of a single cigarette, and contribution of SS from Indian and US cigarettes to ETS appear to be similar. Reduced levels of TPM and nicotine in SS of bidis, probably due to lack of added burning agents, result into relatively higher deliveries of TPM and nicotine in MS as reflected by higher MS/SS values.     

tability Indicating Method for the Analysis of Nicotine in Transdermal Drug Delivery Systems by Means of Gas Chromatography

The delivery of drugs through human skin using transdermal drug delivery (TDD) systems has become an established technology. A popular drug with that dosage form is nicotine for smoking cessation. A stability indicating method for the analysis of nicotine TDDs using gas chromatography (GC) with post-column effluent splitting to a flame ionization detector (FID) and a nitrogen-phosphorus detector (NPD) is described. FID detection gave reliable results with low day-to-day variability. The detector is relatively simple to operate. NPD detection offered enhanced sensitivity and specificity. The combination of both detectors resulted in a rugged method for content analysis with high sensitivity for detection of degradation products at low concentration levels. Despite a relatively simple sample preparation procedure no matrix interferences were observed.     

Polymerization of α-Methylstyrene with Potassium as Initiator. VII. Thermal Decomposition of the Reaction Products

The polymerization of α-methylstyrene, initiated with high concentrations of potassium in tetrahydrofuran and in p-dioxane or with a butyllithium-tetramethylethylenediamine complex in bulk, was carried out at temperatures above 25°C. The resulting products comprising varying proportions of both low (D + A of [Mbar]w = 2.0 to 4.0 × 10³) and high (B + C of [Mbar]W > 20.0 × 10³) molecular weight components were subjected to 50 min isothermal treatments at different temperatures. The poly-α-methylstyrene samples, prepared under the above mentioned solvent-conditions, which had similar proportions of components D + A and B + C, as characterized by gel permeation chromatography and nuclear magnetic resonance showed that their thermal stability decreased with the following order of solvent-conditions: Bulk > p-dioxane > THF. A comparison of the decomposition results obtained with polymers made up of components D + A and B + C and those made up exclusively of component B + C showed that the percent weight-loss and the decrease in molecular weight associated with the latter component B + C is more pronounced when the low molecular weight component D + A is present.     

Quantitation of nicotine in tobacco products by capillary electrophoresis

A simple and rapid capillary electrophoresis (CE) method was developed for the quantitation of nicotine in commercial tobacco products. The method involves a 6 min run at 30 kV, using a 50 mM phosphate buffer (pH 2.5), paraquat as internal standard, and UV detection at 260 nm. Nicotine was extracted from tobacco products in <15 min. Recoveries from spiked extracts were >95%, and the extraction efficiencies of water, 1 M HCI, 1 M acetic acid, 5 mM phosphate buffer (pH 2.5), and 1% triethanol amine were similar. Nicotine concentrations in 67 samples of cigarettes, cigars, and bidis varied between 0.37 and 2.96% (w/w). An established gas chromatography/mass spectrometry method using toluene extraction consistently yielded lower nicotine values than the CE method. Experimental evidence suggests that this is due to insufficient extraction of nicotine by toluene.     

Starker Tobak

The active ingredient of tobacco, nicotine, is originally biosynthesized by plants as a protection against pests. Nicotine survives the harsh conditions in a burning cigarette and binds to certain acetylcholine receptors in the smoker's nerve system within seconds after the first puff. It is the nicotine that makes smoking so extremely addictive. On the other side, the majority of tobacco‐related diseases are not caused by nicotine but by other smoke components. Therefore smoke‐free products like electronic cigarettes have been developed that potentially pose less risk. It is now up to the individual smoker to make an informed choice between different nicotine delivery products and/or smoking at all.     

Simultaneous determination of plasma nicotine and cotinine by UHPLC–MS/MS in C57BL/6 mice and its application in a pharmacokinetic study

Plasma concentrations of nicotine and its active metabolite cotinine are highly correlated with its biological effects. A UHPLC–MS/MS method was developed, validated and applied for nicotine and cotinine analysis in mice plasma. Chromatographic separation was achieved on a BEH HILIC column using acetonitrile (0.1% formic acid) and 10 mm ammonium formate as mobile phase. The gradient elution was performed at 0.4 mL/min with a run time of 3.6 min. The quantitative ion transition was m/z 163.1 > 130.0 for nicotine, m/z 177.1 > 80.0 for cotinine and m/z 167.1 > 134.0 for nicotine‐D₄ (internal standard, IS). For both nicotine and cotinine, the calibration range was 5–500 ng/mL with 5 ng/mL as the lower limit of quantitation, and the intra‐ and inter‐day bias and imprecision were ?4.61–12.00% and <11.12%. The IS normalized recovery was 90.62–98.95% for nicotine and 89.18–101.53% for cotinine, and the IS normalized matrix factor was 106.00–116.44% for nicotine and 100.34–109.85% for cotinine. Both nicotine and cotinine were stable under conventional storage conditions. The validated method has been applied to a pharmacokinetic study in mice to calculate the pharmacokinetic parameters for both analytes.     

示波极谱法烟丝中尼古丁含量测定及电极反应机理

研究了用示波极谱法直接测定烟丝中的尼古丁含量的新方法.在0.2mol/L草酸底液中(pH=4.0),于-1.22V处得到尼古丁的灵敏还原峰,峰电流与尼古丁浓度在1.5～31.5mg/L范围内呈良好的线性关系,检测下限达0.37mg/L.该方法用于烟丝中尼古丁含量的测定,简单快速,测定回收率在91%左右.     

Determination of Cotinine, 3′-Hydroxycotinine,and Their Glucuronides in Urine by Ultra-high Performance Liquid Chromatography

The measurement of the primary nicotine metabolites, cotinine and trans-3′-hydroxycotinine, is a useful biomarker of nicotine exposure and metabolism genetics for smoking cessation research. Herein is described an ultra-high performance liquid chromatography–tandem mass spectrometry method for the determination of these primary nicotine metabolites in urine. Urine samples were diluted one hundred-fold with water and introduced into an ultra-high performance liquid chromatography triple quadrupole mass spectrometer using positive ion electrospray ionization with multiple reaction monitoring. Levels of urinary nicotine metabolites: cotinine, trans-3′-hydroxycotinine, and their respective glucuronides were determined directly using deuterated internal standards and compared with indirect determination by enzymatic hydrolysis. The assay was applied to a community sample of smokers’ urine (n = 280). The assay demonstrated satisfactory performance (relative standard deviation of 1.6–6.5 percent at the 1000 nanograms per milliliter level and >98 percent recovery) suitable for application to smoking studies with a run time less than five minutes. The mean (min-max) levels of cotinine and cotinine-glucuronide were 968 (31-3831) and 976 (9-5607) nanograms per milliliter. The mean (min-max) levels of trans-3′-hydroxycotinine and trans-3′-hydroxycotinine-glucuronide were 3529 (13-21337) and 722 (0-4633) nanograms per milliliter. Direct determination of glucuronide metabolites was superior to indirect measurement using enzymatic hydrolysis, where there was evidence of loss of metabolites during sample preparation. A sensitive and selective ultra-high performance liquid chromatography–tandem mass spectrometry assay was successfully developed for the determination of cotinine, trans-3′-hydroxycotinine, and their glucuronides in urine. The rapid and simple sample preparation makes this assay suitable for high throughput studies involving nicotine metabolism phenotype for both cytochrome P450 2A6 and uridine 5′-diphospho-glucuronosyltransferase, smoking prevalence, and cessation studies.     

Simultaneous determination of four tobacco-specific N-nitrosamines in mainstream smoke for Chinese Virginia cigarettes by liquid chromatography-tandem mass spectrometry and validation under ISO and “Canadian intense” machine smoking regimes

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for determining four tobacco-specific N-nitrosamines (TSNAs) in mainstream smoke from Chinese Virginia cigarettes was developed. Mainstream cigarette smoke particulate matter was collected on a Cambridge filter pad, further extracted using 100 mM ammonium acetate after 100 μL internal standard addition, and subsequently analyzed with LC-MS/MS. The limit of detection for NNN, NNK, NAT and NAB were 0.006, 0.013, 0.003 and 0.021 ng mL⁻¹ respectively, with a linear calibration range spanning 1-200 ng mL⁻¹. Intra- and inter-day precision for four TSNAs ranged from 3.3% to 8.5% and 2.3% to 10.1%; recovery was between 89.1% and 104.9% for Chinese Virginia cigarettes. The proposed method was applied to evaluate TSNAs yields for 39 commercially available cigarettes in Chinese market under ISO and “Canadian intense” machine smoking regimes, on the ground that it comes closest to representing smoke deliveries from human smoking. Total TSNAs emissions are more than double under the Canadian regime. TSNAs:nicotine ratios were used in our assay to show any differences in yield from different brands. TSNAs:nicotine levels show more than a 10-fold difference across brands and types (Chinese Virginia cigarettes and blended cigarettes) in the Chinese market.     

Simultaneous determination of nicotine and 3-vinylpyridine in single cigarette tobacco smoke and in indoor air using direct extraction to solid phase

The aim of the present study was to develop a new analytical method of chromatographic determination of two important markers of ETS exposure: nicotine and 3-vinylpyridine (3-ethenylpyridine, 3-EP) in mainstream (MS) and sidestream (SS) smoke of one single cigarette and in indoor air using direct solid phase extraction combined with gas chromatography. The method can be utilised for both nicotine and 3-EP determination in SS and MS of one single cigarette as well as it allows for a precise determination of compound distribution in indoor air. The application of the same analytical method for both kinds of samples allows anticipating indoor air distribution of both analysed compounds in a very precise way. The precision of the method (calculated as a relative standard deviation) was 9.78% for nicotine and 2.67% for 3-EP; whereas the accuracy (evaluated by a recovery study conducted at three different levels) was 70.1 and 87.3%, respectively. The limit of detection was 0.06 µg per cigarette for both nicotine and 3-EP. The method was evaluated by determining the compounds of interest in two commercially available brands of cigarettes as well as in the reference cigarettes 3R4F and also in indoor air polluted with tobacco smoke. Determined levels of compounds of interest in MS varied from 586 to 772 (nicotine) µg per cigarette and from 3.5 to 10.7 (3-EP) µg per cigarette. In SS smoke the level varied from 14,370 to 22,590 (nicotine) µg per cigarette and from 185 to 550 (3-EP) µg per cigarette, whereas levels in indoor air polluted with tobacco smoke varied from 50.1 to 157.3 (nicotine) µg m^?3and from 7.7 to 20.8 (3-EP) µg m^?3.     

A new spectrofluorometric method for the determination of nicotine base on the inclusion interaction of methylene blue and cucurbit[7]uril

A new method for the fluorometric detection of the nicotine in water is presented. Use of methylene blue (MB) bound to cucurbit[7]uril (CB7) affords the competitive fluorescence inclusion method for the detection of nicotine in aqueous solution. At the same time, the characteristics of host–guest complex between CB7 and MB were studied. It was found that the fluorescence intensity of MB regularly increased upon the addition of CB7. While an appropriate amount of nicotine was added to the MB–CB7 system, the fluorescence intensity of the system quenched remarkably. The method has a linear range of 0.2?～?8.0 μg mL^?1 and a detection of 0.05 μg mL^?1. The method was applied satisfactorily to determine nicotine in cigarettes.     

Monitoring of the smoking process by multicommutation Fourier transform infrared spectroscopy

Nicotine was selected as the target molecule for monitoring of the smoking process by multicommutation Fourier Transform Infrared spectroscopy (FTIR). The method involved the use of CHCl₃ for on-line extraction of nicotine from tobacco, cigarette filters and tobacco ash from NH₄OH alkalinized samples, and absorbance measurement of the characteristic band at 1316 cm⁻¹ in the stopped-flow mode, by obtaining the peak area in the range between 1334 and 1300 cm⁻¹. Under the best operational conditions, the procedure developed provided a detection limit of 0.05 mg mL⁻¹ nicotine, corresponding to 0.5 mg g⁻¹ in the solid sample, a relative standard deviation less than 2.5%, and a sampling frequency of 12 determinations h⁻¹. It can be concluded that nicotine migrates in the smoke mainstream towards the filter during the smoking process. The smoking of cigarettes and cigars is different. Nicotine is retained weakly by both tobacco and filter in the case of cigarettes, and strongly by the unburned tobacco in cigars. The incomplete smoking of cigars and cigarettes reduces nicotine intake and thus reduces the additive effect.     

Determination of synthetic dyes in bean and meat products by liquid chromatography with tandem mass spectrometry

A sensitive and efficient method was developed for the simultaneous determination of eight synthetic dyes (Chrysoidin, Auramine O, Sudan(I–IV), Para Red, and Rhodamine B) in bean and meat products using high‐performance liquid chromatography with tandem mass spectrometry. A simple extraction procedure using acetonitrile has been applied for the extraction of these dyes from spiked bean and meat samples. Chromatographic separation was achieved on a Waters XTerra C₁₈ column (2.1 × 150 mm, 5 μm) with a multistep gradient elution. Detection and quantification were performed using mass spectrometry in multiple reaction monitoring mode. Linear calibrations were obtained with correlation coefficients R² > 0.99. The limits of detection and quantification for the eight dyes were in the ranges of 0.03–0.75 and 0.1–2.0 μg/kg depending on matrices, respectively. The recoveries of these dyes in different food matrices were between 71.2 and 116.9% with relative standard deviations <15.2%, suggesting that the developed method is promising for the accurate quantification of the eight dyes at trace levels in bean and meat products.     

A novel model mouth system for evaluation of <Emphasis Type="Italic">In Vitro</Emphasis>release of nicotine from moist snuff

Background

Pouch moist snuff, as a form of oral smokeless tobacco products, is becoming increasingly popular in North America, Scandinavia (where it is known as Snus), South Asia and parts of Africa. User usually places a pouch between the upper jaw and cheek to obtain euphoria from tobacco, leading to partial intake of tobacco constituents. To evaluate user exposure to tobacco, an approach with a novel model mouth system was developed and applied to evaluate release of nicotine from the pouch.

Results

A novel model mouth system has been developed to evaluate release behavior of tobacco constituents in pouch moist snuff. The system consists of the release medium reservoir module, the flow speed control module, the temperature control module, nicotine release module, and release solution collection module, and simulates buccal condition in terms of temperature, saliva compositions, and the rate of saliva production, etc. Artificial saliva was used as the release medium to evaluate release of nicotine in pouch moist snuff. The optimized test condition was that the release temperature of 37°C and the flow rate performed at 0.2 mL min-1 in the first 5 min and 0.1 mL min-1 in the next 55 min. The performance of the model mouth system was compared with in vivo data of nicotine release in human volunteers. Data from 23 brands of moist snuff indicated that nicotine release rates increased with extraction time and approximately 60-90% of nicotine was released after 30 min of extraction in most of the samples, and the release behavior of nicotine was affected by product weights, nicotine concentration, and product pH, etc.

Conclusion

The model mouth system can be used to evaluate the release behavior of constituents in pouch moist snuff, especially those directly related to human health such as nicotine and tobacco specific nitrosamine (TSNA), etc. This indicated that the system is an alternative tool to evaluate user exposure to tobacco. With further testing and validation, the model mouth system can be applied in risk evaluation of smokeless tobacco products.

Open image in new window

     

Potentiometric determination of nicotine in tobacco products with a nicotine-sensitive liquid membrane electrode

A simple potentiometric method with standard additions is described for the rapid determination of nicotine in tobacco products. A nicotine-sensitive electrode with a liquid membrane of nicotine hydrogen tetra(m-chlorophenyl)borate dissolved in o-nitrotoluene is used. The electrode exhibits near-Nernstian response to monoprotonated nicotine cation activity from 0.08 to 10^-5 M, in the pH range 4–7. Nicotine down to 2 mg per g of sample can be determined with a standard deviation of about 0.5 mg of nicotine. Comparison with an official method gave satisfactory results.     

Measurement of Nicotine in Plasma by High-Performance Liquid Chromatography

Abstract

A new procedure has been developed to measure nicotine in blood plasma by high-performance liquid chromatography (HPLC). Nicotine is extracted from plasma by elution with cholorform. Final determination is achieved by isocratic HPLC with ultraviolet detection. Twenty microliters of plasma extract is deluted over a silica column at a flow rate of 1.0 ml/min with a dioxane:isopropanol:NH₄OH (80:3.0:0.4) mobile phase. The procedure is sensitive to 0.05 ug of nicotine per ml of plasma and is linear within the range of 0.05 to 10.0 ug/ml of plasma. When a known amount of nicotine was added to plasma, the concentration of nicotine measured averaged 99.9 + 3.9 (S.D.)% of the known concentration. The within-sample coefficient of variation was 3.9%     

Radioactivity levels in jurak and moasel,comparison with cigarette tobacco

Jurak and moasel are tobacco products that contain, in addition to tobacco, juice of sugar cane, fruits, spices, tar and nicotine. These products are smoked by hubble-bubble, a popular smoking habit in the Middle Eastern and North African countries. Charcoal is put directly on these products during smoking and the smoke passes through water for cooling purpose before it goes to the lung, without filtering. Radioactivity levels were measured in these products, tobacco leaves, charcoal and in cigarette tobacco of most well known brand names by gamma spectrometry system consisting of HPGe detector coupled to a PC-based 8192 channel multichannel analyzer. The average²²⁶Ra concentrations in jurak, moasel, tobacco leaves, charcoal and cigarette tobacco in Bq/kg were: 3.4, 1.8, 3.2, 2.9 and 7 respectively; that of²³²Th were: 3.8, 2.6, 3.5, 2.2 and 7.8 respectively; that of⁴⁰K were 620, 445, 511, 163 and 876 respectively. It is expected that a jurak smoker inhales 10 times the radioactivity and a moasel smoker twice that compared to a 25 cigarette/d smoker.